Yttrium Alkyl and Benzyl Complexes with Amino−Amidinate

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Organometallics 2000, 19, 3197-3204

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Yttrium Alkyl and Benzyl Complexes with Amino-Amidinate Monoanionic Ancillary Ligands† Sergio Bambirra, Menno J. R. Brandsma, Edward A. C. Brussee, Auke Meetsma, Bart Hessen,* and Jan H. Teuben Center for Catalytic Olefin Polymerization, Stratingh Institute for Chemistry and Chemical Engineering, University of Groningen, Nijenborgh 4, 9747 AG Groningen, The Netherlands Received February 7, 2000

The sequential reaction of YCl3(THF)3.5 with [t-BuC(Ni-Pr)2]Li (Li[A]) and 2 equiv of LiCH(SiMe3)2 gave the mono(amidinate) dialkyl yttrium complex [t-BuC(Ni-Pr)2]Y[CH(SiMe3)2]2(µ-Cl)Li(THF)3 (1), which was structurally characterized. Use of the potentially tridentate amidinate-amine ligands [PhC(NSiMe3)N(CH2)nNMe2]- (n ) 2, B; 3, C) yielded the saltfree dialkyl complexes [PhC(NSiMe3)N(CH2)nNMe2]Y[CH(SiMe3)2]2 (n ) 2, 2a; 3, 2b). A structure determination of 2a showed the tridentate ligand to adopt an approximately meridional geometry. Attempts to prepare analogous benzyl or trimethysilylmethyl complexes with ligand B yielded the ate-complexes Li[PhC(NSiMe3)N(CH2)2NMe2]2Y(R)2 (R ) CH2Ph, 3a; CH2SiMe3, 3b). A crystal structure of 3a showed that the Li ion is encapsulated by two amidinate and two amine nitrogens. The increased spacer length between the amidinate and amine functionalities in ligand C prevented encapsulation of the Li ion, but still produced a bis(amidinate) yttrium benzyl complex, [PhC(NSiMe3)N(CH2)3NMe2]2YCH2Ph (4). In this compound only one of the two dimethylamino functionalities is coordinated to the metal center. Introduction Neutral alkyl complexes of the group 3 metals and lanthanides are highly reactive species that exhibit interesting catalytic properties. Extensive research on the bis(pentamethylcyclopentadienyl) hydrocarbyl and hydride complexes of these metals has revealed their ability to perform catalytic olefin polymerization,1 hydrogenation,2 hydroamination/cyclization,3 C-H activation,1,4 and a range of other catalytic conversions.5 Group 3 metal and lanthanide mono(cyclopentadienyl) dialkyl species were found to be much less easily obtained than the corresponding metallocene monoalkyl †

Netherlands Institute for Catalysis Research (NIOK) Publication No. RUG-00-4-1. (1) (a) Watson, P. L. J. Am. Chem. Soc. 1982, 104, 337. (b) Watson, P. L.; Parshall, G. W. Acc. Chem. Res. 1985, 18, 51. (c) Jeske, G.; Lauke, H.; Mauermann, H.; Swepston, P. N.; Schumann, H.; Marks, T. J. J. Am. Chem. Soc. 1985, 107, 8091. (2) (a) Jeske, G.; Lauke, H.; Mauermann, H.; Schumann, H.; Marks, T. J. J. Am. Chem. Soc. 1985, 107, 8111. (3) Gagne´, M. R.; Stern, C. L.; Marks, T. J. J. Am. Chem. Soc. 1992, 114, 275. (b) Gagne´, M. R.; Brard, L.; Conticello, V. P.; Giardello, M. A.; Stern, C. L.; Marks, T. J. Organometallics 1992, 11, 2003. (c) Li, Y.; Fu, P.-F.; Marks, T. J. Organometallics 1994, 13, 439. (d) Arredondo, V. M.; McDonald, F.; Marks, T. J. Organometallics 1999, 18, 1949, and references therein. (4) Watson, P. L. Chem. Commun. 1983, 276. (b) Thompson, M. E.; Baxter, S. M.; Bulls, A. R.; Burger, B. J.; Nolan, M. C.; Santarsiero, B. D.; Schaefer, W. P.; Bercaw, J. E. J. Am. Chem. Soc. 1987, 102, 203. (c) Ringelberg, S. N.; Meetsma, A.; Hessen, B.; Teuben, J. H. J. Am. Chem. Soc. 1999, 121, 6082. (5) Harrisson, K. N.; Marks, T. J. J. Am. Chem. Soc. 1992, 114, 9220. (b) Watson, P. L.; Tebbe, F. N. US Patent 4,1990,965,386. (c) Forsyth, C. M.; Nolan, S. P.; Marks, T. J. Organometallics 1991, 10, 2543. (d) Molander, G. A.; Julius, M. J. Org. Chem. 1992, 57, 6347. (e) Yasuda, H.; Yamamoto, H.; Yamashita, M.; Yokota, K.; Nakamura, A.; Miyake, S.; Kai, Y.; Kanehisa, N. Macromolecules 1993, 26, 7134. (f) Heeres, H. J.; Teuben, J. H. Organometallics 1991, 10, 1980. (g) Heeres, H. J.; Heeres, A.; Teuben, J. H. Organometallics 1990, 9, 1508. (h) Fu, P.F.; Marks, T. J. J. Am. Chem. Soc. 1995, 117, 10747.

derivatives.6 In particular, the ease of ligand redistribution reactions makes it difficult to obtain these species in pure form. Dialkyl complexes are of interest as potential precursors to cationic group 3 metal and lanthanide alkyls, of which little has been reported as yet and which are expected to be highly reactive.7 Non-cyclopentadienyl ancillary ligands for group 3 metal and lanthanide complexes are receiving increasing attention. Recent examples include mono- and diamide diphosphines,8 deprotonated mono- and diazacrown ethers,7b,9 β-diketiminates,7a,10 and aminotroponiminates.11 In our group, monoanionic benzamidinate (6) Van der Heijden, H.; Pasman, P.; De Boer, E. J. M.; Schaverien, C. J.; Orpen, A. G. Organometallics 1989, 8, 1459. (b) Van der Heijden, H.; Schaverien, C. J.; Orpen, A. G. Organometallics 1989, 8, 255. (c) Heeres, H. J.; Meetsma, A.; Teuben, J. H. J. Chem. Soc., Chem. Commun. 1988, 962. (d) Heeres, H. J.; Meetsma, A.; Teuben, H. J.; Rogers, R. D. Organometallics 1989, 8, 2637. (e) Schumann, H.; Albrecht, I.; Pickardt, J.; Hahn, E. J. Organomet. Chem. 1984, 276, C5. (f) Schumann, H.; Meese-Marktscheffel, J. A.; Dietrich, A. J. Organomet. Chem. 1989, 377, C5. (7) Lee, L. W. M.; Piers, W. E.; Elsegood, M. R. J.; Clegg, W.; Parvez, M. Organometallics 1999, 18, 2947. (b) Lee, L.; Berg, D. J.; Einstein, F. W.; Batchelor, R. J. Organometallics 1997, 16, 1819. (c) Hajela, S.; Schaefer, W. P.; Bercaw, J. E. J. Organomet. Chem. 1997, 532, 45. (d) Schaverien, C. J. Organometallics 1992, 11, 3476. (8) Fryzuk, M. D.; Giesbrecht, G.; Rettig, S. J. Organometallics 1996, 15, 3329. (b) Fryzuk, M. D.; Love, J. B.; Rettig, S. J. J. Am. Chem. Soc. 1997, 119, 9071. (c) Fryzuk, M. D.; Haddad, T. S.; Rettig, S. J. Organometallics 1992, 11, 2967. (d) Fryzuk, M. D.; Haddad, T. S., Rettig, S. J. Organometallics 1991, 10, 2026. (e) Fryzuk, M. D.; Haddad, T. S. J. Am. Chem. Soc. 1988, 110, 8263. (9) Lee, L.; Berg, D. J.; Bushnell, G. W. Organometallics 1995, 14, 8. (10) Hitchcock, P. B.; Lappert, M. F.; Tian, S. J. Chem. Soc., Dalton Trans. 1997, 1945. (b) Drees, D.; Magull, J. Z. Anorg. Allg. Chem. 1995, 621, 941 and 948. (c) Drees, D.; Magull, J. Z. Anorg. Allg. Chem. 1994, 620, 814. (11) Roesky, P. W. Chem. Ber. 1997, 130, 859. (b) Bu¨rgstein, M.; Berberich, H.; Roesky, P. W. Organometallics 1998, 17, 1452. (c) Roesky, P. W. Eur. J. Inorg. Chem. 1998, 593.

10.1021/om0001063 CCC: $19.00 © 2000 American Chemical Society Publication on Web 07/11/2000

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Scheme 1

and alkoxysilylamide ligands were used to explore the chemistry of bis(benzamidinate)12 and bis(alkoxysilylamide)13 yttrium alkyls and hydrides. Preliminary attempts to prepare mono(amidinate) yttrium dialkyls using the N,N′-bis(trimethylsilyl)benzamidinate ligand led to complex product mixtures.14 To obtain these species, either a more sterically hindered amidinate is required or amidinates that can give additional electronic stabilization to the highly electronically unsaturated metal center are required. In this contribution we describe efforts to prepare mono(amidinate) yttrium dialkyl species using the sterically hindered amidinate [t-BuC(Ni-Pr)2]- (A)15 and the N(dimethylaminoalkyl),N′(trimethylsilyl)benzamidinates [PhC(NSiMe3)N(CH2)nNMe2]- (n ) 2, B;16 3, C). These efforts were successful for the sterically demanding alkyl group CH(SiMe3)2, whereas for less bulky alkyls (CH2SiMe3, CH2Ph) ligand redistribution reactions occur to give various bis(amidinate) yttrium alkyl derivatives.

Figure 1. Molecular structure of [t-BuC(Ni-Pr)2]Y[CH(SiMe3)2]2(µ-Cl)Li(THF)3 (1). Table 1. Selected Interatomic Distances (Å) and Angles (deg) for Compound 1 Y-Cl Y-N(1) Y-N(2) Y-C(1) Y-C(8) Li-Cl N(1)-Y-N(2) C(1)-Y-C(8) Cl-Y-N(1) Cl-Y-N(2) Cl-Y-C(1) Cl-Y-C(8)

Results The lithium salt of the amino-amidinate ligand [PhC(NSiMe3)N(CH2)2NMe2]- (B) is obtained by reaction of the lithium silylamide Li[Me2N(CH2)2NSiMe3] with benzonitrile, as was reported previously by our group.16 The analogue with the (CH2)3 spacer between the amidinate and the amine can be obtained similarly from the appropriate silylamide. The use of potassium metal or potassium reagents to deprotonate the silylamines followed by reaction with benzonitrile leads to the analogous potassium salts K[B] and K[C]. It was reported by Roesky et al. that 1 equiv of a potassium aminotroponiminate reacts readily with yttrium trichloride to yield a dimeric mono(aminotroponiminato)yttrium dichloride complex.11a,b We initially attempted to prepare well-defined mono(amidinate) yttrium dichloride starting materials by analogous 1:1 reactions of the lithium or potassium amidinate salts of A, B, and C with YCl3(THF)3.5. These reactions generally yielded (12) Duchateau, R.; Van Wee, C. T.; Meetsma, A.; Van Duijnen, P. Th., Teuben, J. H. Organometallics 1996, 15, 2279. (b) R. Duchateau, Van Wee, C. T.; Meetsma, A.; Teuben, J. H. J. Am. Chem. Soc. 1993, 115, 4931. (13) Duchateau, R.; Tuinstra, T.; Brussee, E. A. C.; Meetsma, A.; Van Duijnen, P. Th.; Teuben, J. H. Organometallics 1997, 16, 3511. (14) Duchateau, R. Ph.D. Thesis, University of Groningen, 1995. (15) Coles, M. P.; Swenson, D. C.; Jordan, R. F.; Young, V. G., Jr. Organometallics 1997, 16, 5183. (16) Brandsma, M. J. R.; Brussee, E. A. C.; Meetsma, A.; Hessen, B.; Teuben, J. H. Eur. J. Inorg. Chem. 1998, 1867.

2.639(2) 2.339(6) 2.353(4) 2.460(7) 2.454(7) 2.362(12) 55.9(2) 116.3(2) 145.33(16) 94.92(14) 93.14(16) 103.71(17)

Li-O(1) Li-O(2) Li-O(3) N(1)-C(18) N(2)-C(18) Y-Cl-Li Y-C(1)-Si(1) Y-C(1)-Si(2) Si(1)-C(1)-Si(2) Y-C(8)-Si(3) Y-C(8)-Si(4) Si(3)-C(8)-Si(4)

1.921(13) 1.905(12) 1.926(13) 1.340(9) 1.335(9) 167.2(3) 123.4(3) 110.4(3) 117.9(4) 118.0(3) 122.8(3) 112.5(4)

noncrystalline products with poorly defined stoichiometries. For the preparation of mono(amidinate)yttrium dialkyls we therefore made use of a reaction sequence in which initially YCl3(THF)3.5 is reacted in THF with 1 equiv of the appropriate amidinate salt, followed by subsequent additon of 2 equiv of the alkylating agent. Such a sequential reaction of YCl3(THF)3.5 with [t-BuC(Ni-Pr)2]Li (Li[A])15 and 2 equiv of Li[CH(SiMe3)2] in THF afforded, after pentane extraction and crystallization, large crystals of the mono(amidinate)-dialkyl complex [t-BuC(Ni-Pr)2]Y[CH(SiMe3)2]2(µ-Cl)Li(THF)3 (1, Scheme 1) in 83% isolated yield. An X-ray structure determination of 1 (Figure 1, selected interatomic distances and angles in Table 1) shows the practically linear coordination of LiCl to the yttrium center, with three (disordered) THF molecules completing the coordination sphere of Li. The linear bonding of an alkalimetal halide to a metal center has been observed on several occasions in lanthanide hydrocarbyl complexes where the steric bulk of the ligands is insufficient to shield the lanthanide metal coordination sphere.17 As in the bis(amidinate) yttrium complexes,12 the bite angle of the N,N′-σ2 amidinate ligand is very small (N(1)Y-N(2) ) 55.9(2)°). The Y-C(alkyl) distances are close to those observed in other Y-CH(SiMe3)2 complexes.12,13,18,19 In the solid state the alkyl groups are rotated relative to each other (dihedral angles C(1)-Y-C(8)(17) Atwood, J. L.; Lappert, M. F.; Smith, R. G.; Zhang, H. J. Chem. Soc., Chem. Commun. 1988, 1308. (b) Schaverien, C. J.; Van Mechelen, J. B. Organometallics 1991, 10, 1704.

Yttrium Alkyl and Benzyl Complexes

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Scheme 2

Si(3) ) -86.2(4)°, C(8)-Y-C(1)-Si(1) ) 22.3(5)°) to minimize the steric repulsion between the two bulky groups. This is also observed in the ate-complex [(THF)Li(µ-Ot-Bu)2]Y[CH(SiMe3)2]2, in which the yttrium is four-coordinate.19 In some yttrium and lanthanide -CH(SiMe3)2 complexes (e.g., Cp*2LnCH(SiMe3)21c,18 and Cp*La[CH(SiMe3)2]26b-d) a strong distortion of the alkyl Y-C-Si angles is observed that stems from an interaction of the β-Si-C bond with the metal center.20 In complex 1 no such distortion of the Y-C-Si angles is present. This interaction was also absent from the bis(amidinate) and bisalkoxysilylamido yttrium-CH(SiMe3)2 complexes.12,13 Solution NMR spectra of 1 at ambient temperature show equivalent alkyl SiMe3 and i-Pr methyl groups, implying fluxional behavior. Cooling a toluene-d8 solution of 1 leads to broadening of the resonances, but at -90 °C the slow exchange limit had not yet been reached. The 1H and 13C NMR characteristics of the Y-alkyl CH-moiety are close to those of the bis(amidinate) complex [PhC(NSiMe3)2]2YCH(SiMe3)212 and differ from those in Cp*2YCH(SiMe3)2,18 in which the 13C NMR resonance is found considerably more upfield (δ 25.2 ppm, compared to 44.1 ppm in 1). The coordination of 1 equiv of LiCl to the yttrium center of 1 suggests that the amidinate employed provides insufficient protection to the metal center. To prevent incorporation of alkalimetal halide, a similar synthesis was performed with the lithium salts of the potentially tridentate amino-amidinates [PhC(NSiMe3)N(CH2)nNMe2]- (n ) 2, B; 3, C). After recrystallization from pentane, these reactions afforded the saltfree mono(amidinate)-dialkyls [PhC(NSiMe3)N(CH2)nNMe2]Y[CH(SiMe3)2]2 (n ) 2, 2a; 3, 2b) in modest isolated yield (Scheme 2). The derivative with n ) 2 (2a) was characterized by single-crystal X-ray diffraction. The structure (Figure 2, selected interatomic distances and angles in Table 2) shows that the amino-amidinate ligand is indeed tridentate, with the ligand adopting an approximately meridional coordination mode. This contrasts with the facial tridentate coordination mode that was observed for this ligand in the vanadium(III) complex [PhC(NSiMe3)N(CH2)2NMe2]VCl2(THF).16 The coordination sphere of Y in 2a is directly related to that in 1, with the main difference that the N(3)-Y-N(2) angle in 2a (66.6(2)°) is considerably smaller than the Cl-Y-N(2) angle of 94.9(2)° in 1. The NMR spectral features of the Y-alkyl moieties in 2 are very similar to those of 1, but showing varying degrees of fluxionality at ambient temperature. For 2a there are clearly two separate alkyl SiMe3 resonances, whereas for 2b one broad alkyl SiMe3 resonance is observed. Warming the (18) Den Haan, K. H.; De Boer, J. L.; Teuben, J. H.; Spek, A. L.; Kojic-Prodic, B.; Hays, G. R.; Huis, R. Organometallics 1986, 5, 1726. (19) Evans, W. J.; Broomhall-Dillard, R. N. R.; Ziller, J. W. Organometallics 1996, 15, 1351. (20) Klooster, W. T.; Brammer, L.; Schaverien, C. J.; Budzelaar, P. H. M. J. Am. Chem. Soc. 1999, 121, 1381.

Figure 2. Molecular structure of [PhC(NSiMe3)N(CH2)2NMe2]Y[CH(SiMe3)2]2 (2a). Table 2. Selected Interatomic Distances (Å) and Angles (deg) for Compound 2 Y-N(1) Y-N(2) Y-N(3) Y-C(11) Y-C(18) N(1)-Y-N(2) N(2)-Y-N(3) N(1)-Y-N(3) C(11)-Y-C(18) N(3)-Y-C(11) N(3)-Y-C(18)

2.366(3) 2.284(4) 2.576(4) 2.425(5) 2.471(4) 57.75(12) 66.57(12) 119.76(12) 118.17(15) 108.46(13) 108.37(13)

N(1)-C(1) N(2)-C(1)

Y-C(11)-Si(3) Y-C(11)-Si(4) Si(3)-C(11)-Si(4) Y-C(18)-Si(5) Y-C(18)-Si(6) Si(5)-C(18)-Si(6)

1.345(6) 1.327(5)

119.2(2) 114.4(2) 115.2(2) 122.9(2) 116.9(2) 115.8(2)

sample of 2a leads to coalescence of the two alkyl SiMe3 resonances around 50 °C. The increase in amidinateamine spacer length on going from 2a to 2b leads only to slight downfield shifts of the Y-CH 1H and 13C NMR resonances. The successful synthesis of compounds 2 has shown that the use of the tridentate amino-amidinate monoanionic ligand enables the isolation of monomeric, saltfree mono(amidinate)-dialkyl yttrium species. The bulky alkyl group employed, bis(trimethylsilyl)methyl, is very suitable for obtaining stable, highly electrondeficient alkyl species, but rather disadvantageous for further reactivity studies. We therefore applied the same synthesis strategy to try and isolate dialkyl species with less sterically encumbered alkyl groups, viz., trimethylsilylmethyl and benzyl. The sequential reactions of YCl3(THF)3.5 with 1 equiv of Li[PhC(NSiMe3)N(CH2)2NMe2] (Li[B]) and 2 equiv of Me3SiCH2Li or PhCH2K resulted in relatively low yields of products with an amino-amidinate-to-alkyl ratio of 1:1 (as seen by NMR). A crystal structure determination of the benzyl derivative (vide infra) showed that these products are in fact bis(amino-amidinate) yttrium atecomplexes of the type Li[PhC(NSiMe3)N(CH2)2NMe2]2Y(R)2 (R ) CH2Ph, 3a; CH2SiMe3, 3b). They are obtained in significantly higher yields when the appropriate amino-amidinate-to-yttrium ratio of 2:1 is used in the synthesis (Scheme 3). A crystal structure determination of Li[PhC(NSiMe3)N(CH2)2NMe2]2Y(CH2Ph)2 (3a) showed two independent molecules of 3a in the unit cell that differ mainly by the orientation of the benzyl groups (rotation

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Figure 3. Molecular structure of Li[PhC(NSiMe3)N(CH2)2NMe2]2Y(CH2Ph)2 (3a). Only one of the two independent molecules is shown.

Figure 4. Molecular structure of [PhC(NSiMe3)N(CH2)3NMe2]2YCH2Ph (4). Scheme 4

Scheme 3

Table 3. Selected Interatomic Distances (Å) and Angles (deg) for Compound 3 (molecule 1 of the asymmetric unit only) Y(1)-N(1) Y(1)-N(2) Y(1)-N(4) Y(1)-N(5) Y(1)-C(1) N(1)-C(18) N(2)-C(18) C(1)-Y(1)-C(8) Y(1)-C(1)-C(2) Y(1)-C(8)-C(9) N(1)-Y(1)-C(1) N(1)-Y(1)-C(8) N(2)-Y(1)-C(1) N(2)-Y(1)-C(8)

2.431(5) 2.450(7) 2.403(7) 2.476(6) 2.490(8) 1.349(10) 1.333(10) 105.1(3) 109.1(5) 119.7(5) 100.2(2) 91.3(2) 86.6(2) 146.6(2)

Li(1)-N(2) Li(1)-N(3) Li(1)-N(5) Li(1)-N(6) Y(1)-C(8) N(4)-C(32) N(5)-C(32) N(1)-Y(1)-N(2) N(1)-Y(1)-N(4) N(1)-Y(1)-N(5) N(2)-Li(1)-N(3) N(2)-Li(1)-N(5) N(3)-Li(1)-N(5) N(5)-Li(1)-N(6)

2.109(13) 2.039(14) 2.036(14) 2.045(13) 2.463(6) 1.346(10) 1.283(10) 55.5(2) 145.4(2) 95.3(2) 87.3(5) 104.1(6) 134.5(6) 88.9(5)

around the Y-CH2 axis). In Figure 3 only one of the two independent molecules is shown (molecule 1, selected interatomic distances and angles in Table 3). Molecule 2 is somewhat more “regular” in that it approaches (noncrystallographic) C2 symmetry. In 3a two amino-amidinate ligands are bound to yttrium, but the ligand dimethylamino functionalities are coordinated to a Li+ ion that is further ligated by the alkylsubstituted amidinate nitrogens. These nitrogen atoms, N(2) and N(5) in Figure 3, are thus bound to both yttrium and lithium and create, together with the dimethylamino nitrogens, a distorted tetrahedral site for the lithium ion. Two benzyl ligands are bound to yttrium, and the complex can be described as a zwitterion with a Li cation and a bis(amidinate) yttrium dibenzyl anion. The two benzyl groups are essentially η1-bound, and neither the crystal structure nor the NMR spectra (benzyl methylene 1JCH ) 117.1 Hz) present evidence for additional interaction of the benzyl groups

with the metal center. The Li site is distorted tetrahedral, with the smallest N-Li-N angles (around 88°) for the pairs of chelating nitrogens, N(2)/N(3) and N(5)/N(6). The solution NMR spectra indicate effective C2 symmetry, showing an ABX pattern for the benzyl methylene protons in 3a, whereas the alkyl methylene proton resonances in 3b appear to be accidentally degenerate. It is thus observed that a reduction of alkyl group size from bis(trimethylsilyl)methyl to trimethylsilylmethyl or benzyl leads to the formation of bis(amino-amidinate) yttrium complexes through ligand redistribution. It is difficult to say a priori if this is an effect intrinsic to the size reduction of the alkyl group or that this is induced by the “incarceration” of the lithium ion in the four-coordinate site that is created by the two aminoamidinate ligands and that seems particularly suitable to bind lithium. To test this, we performed two experiments in which the binding of the alkali metal ion should be disfavored: (a) an increase in spacer length in the amino-amidinate from (CH2)2 to (CH2)3, to increase the size of the cage, and (b) the use of the (CH2)2 spacer with a larger alkali metal ion, potassium. The reaction of YCl3(THF)3.5 with 1 equiv of Li[PhC(NSiMe3)N(CH2)3NMe2] (Li[C]) and 2 equiv of PhCH2K resulted in a relatively low yield of the salt-free bis(amino-amidinate) yttrium benzyl complex [PhC(NSiMe3)N(CH2)3NMe2]2YCH2Ph (4). Again, this compound could be obtained in a higher isolated yield when the appropriate amidinate-to-yttrium-to-benzyl ratio of 2:1:1 was employed (Scheme 4). Slow crystallization from pentane yielded single crystals of stoichiometry 4‚(pentane)0.5 suitable for X-ray diffraction. The structure of 4 (Figure 4, selected interatomic distances and angles in Table 4) shows that two amino-amidinates are bound to yttrium, but that the dimethylamino group of only one of the ligands is coordinated to the metal center. This tridentate ligand adopts a meridional coordination mode. The benzyl group in the 12-electron complex 4 exhibits a more acute Y-CH2-Cipso angle (96.3(3)°) than the benzyl groups in 3a, but still not as

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Organometallics, Vol. 19, No. 16, 2000 3201

Table 4. Selected Interatomic Distances (Å) and Angles (deg) for Compound 4 Y-N(1) Y-N(2) Y-N(4) Y-N(5) Y-N(6) Y-C(16) N(1)-Y-N(4) N(1)-Y-N(5) N(1)-Y-N(6) N(1)-Y-C(16) N(2)-Y-N(5)

2.367(4) 2.394(4) 2.363(4) 2.358(4) 2.539(4) 2.487(6) 94.41(13) 104.72(14) 94.51(13) 133.20(18) 157.17(15)

N(1)-C(1) N(2)-C(1) N(4)-C(23) N(5)-C(23)

N(4)-Y-N(5) N(5)-Y-N(6) N(4)-Y-N(6) N(6)-Y-C(16) Y-C(16)-C(17)

1.339(6) 1.315(6) 1.326(6) 1.327(6)

57.05(13) 76.78(13) 133.73(13) 115.03(17) 96.3(3)

Scheme 5

pronounced as in, for example, Cp*2CeCH2Ph (86°).21 The benzyl methylene CH coupling constant of 121.9 Hz is somewhat larger that that observed for 3a. The above result clearly suggests that encapsulation of the alkali metal ion is not the driving force for the formation of bis(amino-amidinate) yttrium alkyl complexes when relatively small alkyl groups are employed. In addition we performed the reaction of YCl3(THF)3.5 with 1 equiv of K[PhC(NSiMe3)N(CH2)2NMe2] (K[B]) and 2 equiv of PhCH2K. This resulted in a relatively low yield of a compound that, based on 1H and 13C NMR data, was identified as the THF adduct of the bis(amino-amidinate) yttrium benzyl complex, [PhC(NSiMe3)N(CH2)2NMe2]2YCH2Ph(THF) (5, Scheme 5). It thus appears that in the bis(amino-amidinate) complexes the (CH2)2 spacer renders intramolecular coordination of the dimethylamino functionality less favorable; in this case coordination of one molecule of THF is preferred. Again, this compound is obtained more conveniently (with an isolated yield of 60%) when the correct stoichiometry of the reagents is used. Discussion Using the amidinate anionic functionality, it proved possible to prepare highly electron-deficient (10-electron) yttrium dialkyl species of the type (amidinate)Y(L)[CH(SiMe3)2]2, where L is a Lewis base (either (THF)3LiCl in 1 or a tethered dimethylamino group in 2). In these complexes the amidinate and L functionalities are arranged in an approximately meridional geometry. Interestingly, for yttrium and the small lanthanide lutetium the isoelectronic dialkyls Cp*M[CH(SiMe3)2]2 could not be obtained, although they are available for the larger lanthanides La and Ce.6b-d The meridional arrangement of the ancillary ligands in 1 and 2 allows a different orientation of the two large alkyl groups relative to each other than in the Cp* complexes, thus relieving steric hindrance around the metal center. Although bis(amidinate)YCH(SiMe3)2 complexes are known,12 formation of bis(amidinate)complexes was not (21) Booij, M.; Meetsma, A.; Teuben, J. H. Organometallics 1991, 10, 3246.

found to pose difficulties in the synthesis of the mono(amidinate) CH(SiMe3)2 complexes 1 and 2. This did occur in attempts to prepare mono(amidinate) complexes with smaller metal-bound alkyl groups. It remains to be seen if such compounds themselves are inherently unstable or if disproportionation is brought about by the presence of alkalimetal halide. There is precedent for the promotion of ligand scrambling by alkalimetal halides.22 In the first transition metal complex of the aminoamidinate ligand B, the V(III) complex [PhC(NSiMe3)N(CH2)2NMe2]VCl2(THF),16 a facial η3-coordination mode was observed. This was surprising, as it necessitated strong nonplanarity of the dimethylaminoethyl-substituted amidinate nitrogen (the sum of the angles around this nitrogen atom is 336.4°). The structure of the yttrium complex 2 shows that this amino-amidinate ligand can also readily adopt a meridional η3-coordination mode when the metal center is larger and less specific for an octahedral complex geometry. But even in these compounds it is seen that the alkyl-substituted amidinate nitrogen is not as rigorously planar as the SiMe3-substituted amidinate nitrogen is. The sums of the angles around the alkyl-substituted amidinate nitrogens are 349.3° in 2 and 359.3° and 352.6° in 4. It was seen in the structure of the ate-complex 3a that the ligand can also support the formation of bimetallic complexes (in this case with one amidinate nitrogen bound to Y, the other one bridging between Y and Li, and with the amine nitrogen bound to Li). It thus appears that the amino-amidinate ancillary ligand is quite versatile in its coordination modes, and we expect interesting results from the chemistry of this ligand with other transition metals and lanthanides. Conclusions Mono(amidinate) yttrium dialkyls (amidinate)YR2(L) (L ) Lewis base) are accessible via salt methathesis for R ) CH(SiMe3)2. An amine Lewis base can be incorporated into the ancillary ligand to give salt- and solventfree dialkyls (amidinate-amine)YR2. Use of alkyl groups smaller than bis(trimethylsilyl) leads to ligand redistribution to give bis(amidinate) yttrium complexes. In the case of the amidinate-amine ancillary ligands, a fitting match between the spacer linking the amidinate and amine functionalities and the alkalimetal ion can lead to ate-complexes of the type (alkalimetal)(amidinate-amine)2YR2. Experimental Section All experiments were performed under nitrogen atmosphere using standard glovebox and Schlenk techniques. Deuterated solvents (Aldrich) were dried over Na/K alloy and vacuum transferred before use (C6D6, THF-d8). Toluene, THF, diethyl ether, and pentane were distilled from Na or Na/K alloy before use. The compounds [t-BuC(Ni-Pr)2]Li15 and Li[B],16 YCl3(THF)3.5,23 Me2N(CH2)2N(H)SiMe3,16 PhCH2K,24 Me3SiCH2Li,25 (22) For examples in cyclopentadienyl lanthanide chemistry see references cited in: Schumann, H.; Meese-Marktscheffel, J. A.; Esser, L. Chem. Rev. 1995, 95, 865. (23) Freeman, J. H.; Smith, M. L. J. Inorg. Nucl. Chem. 1958, 7, 224. (24) Lochmann, L.; Trekoval, J. J. Organomet. Chem. 1987, 326, 1. (25) Negishi, E.; Swanson, D. R.; Rousset, C. J. J. Org. Chem. 1990, 55, 5406.

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and (Me3Si)2CHLi26 were prepared according to literature procedures. Benzonitrile (Aldrich) was degassed and dried over molecular sieves (4 Å) before use. The diamines Me2N(CH2)nNH2 (n ) 2, 3; Aldrich) were used as purchased. NMR spectra were run at ambient temperature on a Varian VXR-300 spectrometer unless mentioned otherwise. Elemental analyses were performed by the Microanalytical Department of the University of Groningen. Every value is the average of at least two independent determinations. In many of the complexes the carbon contents found are consistently and reproducibly too low relative to the calculated values (by 0.5% to up to 1.8% absolute), whereas for the other elements correct values are obtained. It is possible that formation of inert carbides (especially of Si) is responsible for this. [t-BuC(Ni-Pr)2]Y[CH(SiMe3)2]2LiCl(THF)3 (1). Solid Li[A] (0.23 g, 1.21 mmol) was added to a suspension of YCl3(THF)3.5 (0.53 g, 1.20 mmol) in THF (20 mL) at -40 °C. The mixture was allowed to warm to room temperature and was stirred overnight. The resulting solution was cooled to -40 °C, and solid LiCH(SiMe3)2 (0.39 g, 2.40 mmol) was added. After stirring for 5 h at -10 °C the solvent was removed in vacuo, and the residue was stripped of remaining THF by stirring with pentane (2 × 5 mL), which was subsequently pumped off. Extraction with pentane (3 × 30 mL), concentrating, and cooling to -20 °C yielded 1 (0.85 g, 0.98 mmol, 83%) as white crystals. 1H NMR (300 MHz, C6D6): δ 4.01 (sept, 3JHH ) 6.3 Hz, 2 H, CHMe2), 3.57 (m, 12 H, THF), 1.43 (m, 12 H, THF), 1.20 (d, 3JHH ) 6.3 Hz, 12 H, CHMe2), 1.14 (s, 9 H, CMe3) 0.35 (s, 36 H, CH(SiMe3)2), -0.87 (d, 2JYH ) 2.1 Hz, 2 H, CHSiMe3). 13C{1H} NMR (75.4 MHz, C D ): δ 178.3 (CCMe ), 68.2 (THF), 6 6 3 46.8 (CHMe2), 44.1 (d, 1JYC ) 31.7 Hz, CHSiMe3) 31.4 (CMe3), 27.5, (CHMe2), 5.8 (CHSiMe3). Anal. Calcd for C37H85O3N2YLiClSi4 (848.45): C, 52.30; H, 10.08; N, 3.30; Y, 10.46. Found: C, 51.18; H, 10.03; N, 2.86; Y, 10.43. Me2N(CH2)3NHSiMe3. This diamine was prepared according to the procedure described for the (CH2)2-bridged analogue.16 To a solution of Me2N(CH2)2NH2 (8 g, 80.0 mmol) and Et3N (38 mL, 270 mmol) in dioxane (50 mL) was added Me3SiCl (11.6 mL, 80 mmol). The resulting white suspension was then warmed to 95 °C and stirred overnight at this temperature. After filtration and extraction of the remaining white solid with ether (2 × 100 mL) the solvents were removed in vacuo from the combined filtrate and extracts. A distillation of the remaining liquid under reduced pressure (80 mmHg, 70-75 °C) gave Me2N(CH2)3NHSiMe3 as a colorless liquid (11.7 g, 66.4 mmol, 83%). 1H NMR (300 MHz, C6D6): δ 2.72 (t, 3JHH ) 3.9 Hz, 2 H, NCH2(CH2)2NMe2), 2.18 (t, 3JHH ) 3.9 Hz, 2 H, NCH2CH2CH2NMe2), 2.08 (s, 6 H, NMe2), 1.45 (m, 2 H, NCH2CH2CH2NMe2), 0.07 (s, 9 H, NSiMe3). Li[PhC(N(CH2)3NMe2)(NSiMe3)] (Li[C]). A solution of Me2N(CH2)3NHSiMe3 (11.7 g, 66.4 mmol) in ether (50 mL) was cooled to 0 °C, and 26.5 mL of 2.5 M BuLi/hexane was added dropwise. After stirring for 3 h, the mixture was warmed to ambient temperature, and benzonitrile (6.7 mL, 66.0 mmol) was added. The yellow reaction mixture was stirred overnight, after which the solvent was removed in vacuo to give an orange oil, which slowly solidified. Washing with pentane gives Li[C] (13.0 g, 53.4 mmol, 81.0%) as a yellow solid. 1H NMR (300 MHz, C6D6): δ 7.05 (m, 5 H, Ar), 2.89 (t, 3JHH ) 5.1 Hz, 2 H, NCH2(CH2)2NMe2), 2.17 (br t, 2 H, NCH2CH2CH2NMe2), 1.98 (s, 6 H, NMe2), 1.25 (qui, 3JHH ) 5.4 Hz, 2 H, NCH2CH2CH2NMe2), 0.10 (s, 9 H, NSiMe3). 13C NMR (75.4 MHz, C6D6): δ 177.5 (CPh), 143.7 (Ph Cipso), 129.2 (d, J ) 158.6 Hz, o-Ph), 126.6 (d, J ) 159 Hz, p-Ph and m-Ph), 60.4 (t, J ) 131.7 Hz, NCH2(CH2)2NMe2), 50.0 (t, J ) 130.6 Hz, N(CH2)2CH2NMe2), 46.2 (q, J ) 134.2 Hz, NMe2), 29.0 (t, J ) 124.4 Hz, NCH2CH2CH2NMe2), 3.2 (q, J ) 117.2 Hz, NSiMe3). Anal. Calcd for C15H26N3SiLi (283.41): C, 63.57; H, 9.25; N, 14.83; Li, 2.45. Found: C, 63.57; H, 9.30; N, 14.56; Li, 2.34. (26) Wiberg, N.; Wagner, G. Chem. Ber. 1986, 119, 1455.

Bambirra et al. [PhC(N(CH2)2NMe2)(NSiMe3)]Y[CH(SiMe3)2]2 (2a). Solid Li[B] (0.33 g, 1.2 mmol) was added to a suspension of YCl3(THF)3.5 (0.53 g, 1.2 mmol) in THF (30 mL) at -40 °C. The reaction mixture was allowed to warm to room temperature and was stirred overnight. The resulting solution was cooled to -40 °C and treated with LiCH(SiMe3)2 (0.40 g, 2.4 mmol). After stirring for 3 additional hours at -10 °C, the solvent was removed in vacuo. The residue was stripped of remaining THF by stirring with pentane (2 × 5 mL), which was subsequently removed in vacuo. Extraction with pentane (3 × 30 mL) and cooling to -20 °C yielded 2a (0.23 g, 0.34 mmol, 29%) as white crystals. The low isolated yield appears to be due to the high solubility of the product. 1H NMR (300 MHz, C6D6): δ 7.16 (m, 2 H, Ar), 7.06 (m, 3 H, Ar), 2.71 (t, 3JHH ) 5.8 Hz, 2 H, NCH2CH2NMe2), 2.14 (s, 6 H NMe2), 2.02 (t, 3JHH ) 5.8 Hz, 2 H, NCH2CH2NMe2), 0.41 (s, 18 H, YCH(SiMe3)2), 0.38 (s, 18 H, YCH(SiMe3)2), 0.17 (s, 9 H, NSiMe3), -1.00 (d, 9 H, 2JYH ) 2.2 Hz, YCH(SiMe3)2). 13C NMR (75.4 MHz, C6D6): δ 179.7 (s, NN′CPh), 137.5 (s, Ph Cipso), 129.3 (d, J ) 153.7 Hz, o-Ph), 128.5 (d, J ) 147.3 Hz, m-Ph), 126.8 (d, J ) 158.6 Hz, p-Ph), 62.6 (t, J ) 135.4 Hz, NCH2CH2NMe2), 45.8 (q, J ) 135.4 Hz, NMe2), 44.2 (t, J ) 135.4 Hz, NCH2CH2NMe2), 41.4 (dd, 1JYC ) 32.9, 1JCH ) 89.0 Hz, YCH(SiMe3)2), 5.9 (q, J ) 117.0 Hz, YCH(SiMe3)2), 6.0 (q, J ) 117.1 Hz, YCH(SiMe3)2), 3.3 (q, J ) 118.3 Hz, NSiMe3). Anal. Calcd for C28H62N3Si5Y (669.28): C, 50.20; H, 9.34; N, 6.28; Y, 13.28. Found: C, 49.91; H, 9.43; N, 5.86; Y, 12.95. [PhC(N(CH2)3NMe2)(NSiMe3)]Y[CH(SiMe3)2]2 (2b). A procedure analogous to the one described for 2a above, using Li[C] (0.18 g, 0.62 mmol) and YCl3(THF)3.5 (0.28 g, 0.62 mmol) in 30 mL of THF, yielded 0.12 g (0.17 mmol, 29%) of 2b as white crystals. 1H NMR (300 MHz, C6D6): δ 7.17 (m, 2 H, Ph), 7.04 (m, 3 H, Ph), 2.60 (t, 3JHH ) 5.8 Hz, 2 H, NCH2(CH2)2NMe2), 2.18 (s, 6 H NMe2), 2.01 (t, 3JHH ) 5.1 Hz, 2 H, N(CH2)2CH2NMe2), 1.15 (br p, 2 H, NCH2CH2CH2NMe2) 0.40 (br, 36 H, YCH(SiMe3)2), 0.17 (s, 9 H, NSiMe3), -0.89 (d, 9 H, 13 2JYH ) 2.2 Hz, YCH(SiMe3)2). C NMR (75.4 MHz, C6D6): δ 181.4 (s, CPh), 137.5 (s, Ph Cipso), 128.6 (d, J ) 161.0 Hz, o-Ph), 127.9 (m-Ph, partially overlapped), 125.9 (d, J ) 159.7 Hz, p-Ph), 62.7 (t, J ) 128.1 Hz, NCH2(CH2)2NMe2), 47.0 (t, J ) 134.2 Hz, N(CH2)2CH2NMe2), 46.5 (q, J ) 136.7 Hz, NMe2), 43.4 (dd, 1JYC ) 32.9 Hz, 1JCH ) 87.9 Hz, YCH), 26.0 (t, J ) 125.6 Hz, NCH2CH2CH2NMe2), 6.5 and 6.2 (br q each, J ) 117 Hz, YCH(SiMe3)2), 3.3 (t, J ) 118.3 Hz, NSiMe3). Li[PhC(NSiMe3)N(CH2)2NMe2]2Y(CH2Ph)2 (3a). Solid Li[B] (0.10 g, 0.4 mmol) was added to a suspension of YCl3(THF)3.5 (0.09 g, 0.2 mmol) in THF (20 mL) at ambient temperature. After stirring for 2 h the resulting solution was cooled to -40 °C and KCH2Ph (0.6 g, 0.4 mmol) was added. The orange mixture was stirred for 2 h, then warmed to ambient temperature. The solvent was removed in vacuo, and the resulting orange oil was rinsed with pentane (10 mL). Extraction with toluene (3 × 30 mL), concentration of the extracts, and cooling to -20 °C gave 3a (0.12 g, 0.15 mmol, 74%) as a yellow microcrystalline material. A reaction of YCl3(THF)3.5 (0.13 g, 0.3 mmol) and Li[B] (0.08 g, 0.3 mmol) with 2 equiv of KCH2Ph (0.08 g, 0.6 mmol) under otherwise similar conditions yielded 0.07 g of 3a (28%). 1H NMR (300 MHz, C6D6): δ 7.3 (m, 8 H, Ph), 7.21 (br t, 2 H, Ph), 7.08 (m, 4 H, Ph), 6.88 (m, 2 H, Ph), 6.76 (m, 4 H, Ph), 2.8 (m, 6 H, NCH2CHHNMe2), 2.42 (dd, 2JHH ) 8.6 Hz, 2JYH ) 3.3 Hz, 2 H, YCH2Ph), 2.31 (dd, 2JHH ) 8.6 Hz, 2JYH ) 2.7 Hz, 2 H, YCH2Ph), 1.92 (s, 6 H NMe2), 1.57 (m, 2 H, NCH2CHHNMe2), 1.48 (s, 6 H, NMe2), 0.06 (s, 18 H, NSiMe3). 13C NMR (75.4 MHz, C6D6): δ 181.9 (s, NN′CPh), 155.0 (s, Ph Cipso), 138.7(s, Ph Cipso), 129.8 (d, J ) 161.1 Hz, Ph CH), 129.0 (d, J ) 153.8 Hz, Ph CH), 128.7 (d, J ) 155.0 Hz, Ph CH), 124.7 (d, J ) 154.9 Hz, Ph CH), 124.3 (d, J ) 150.1 Hz, Ph CH), 116.4 (d, J ) 157.3 Hz, Ph CH), 60.4 (t, J ) 131.9 Hz, NCH2CH2NMe2), 53.9 (d, 1JYC ) 32.9 Hz, t, 1JCH ) 117.1 Hz, YCH2Ph), 45.9 (t, J ) 136.7 Hz, NCH2CH2NMe2) 45.9 (q, J ) 137.9 Hz, NMe2), 42.1

Yttrium Alkyl and Benzyl Complexes (q, J ) 131.7 Hz, NMe2), 3.1 (q, J ) 118.4 Hz, NSiMe3). Anal. Calcd for C42H62N6Si2YLi (803.01): C, 62.82; H, 7.78; N, 10.47; Y, 11.07; Li, 0.86. Found: C, 60.91; H, 8.14; N, 10.30; Y, 10.90; Li, 0.79 Li[PhC(NSiMe3)N(CH2)2NMe2]2Y(CH2SiMe3)2 (3b). A suspension of YCl3(THF)3.5 (0.13 g, 0.3 mmol) in THF (20 mL, -40 °C) was treated with Li[B] (0.08 g, 0.3 mmol). The resulting pale yellow solution was allowed to warm to room temperature and was stirred overnight. Subsequently the mixture was cooled to -40 °C, and LiCH2SiMe3 (0.03 g, 0.3 mmol) was added. After warming to room temperature, the solution was stirred for 2 h. The solvent was removed in vacuo, and the residual THF removed by stirring twice with pentane (5 mL), which was then pumped off. The mixture was extracted with pentane (2 × 30 mL). Concentration and cooling to -20 °C afforded 3b (0.09 g, 0.1 mmol, 37%) as white crystals. 1H NMR (300 MHz, C6D6): δ 7.78 (d, 2 H, 3JHH ) 7.3 Hz, o-Ph), 7.21 (t, 2 H, 3JHH ) 7.3 Hz, m-Ph), 7.12 (t, 2 H, 3JHH ) 7.6 Hz, m-Ph), 7.07 (t, 2 H, 3JHH ) 7.3 Hz, p-Ph), 6.87 (d, 3JHH ) 6.9 Hz, 2 H, o-Ph), 2.8 (m, 6 H, NCH2CHHNMe2), 1.94 (s, 6 H NMe2), 1.53 (m, 2 H, NCH2CHHNMe2), 1.48 (s, 6 H, NMe2), 0.61 (s, 18 H, CH2SiMe3), 0.21 (s, 18 H, NSiMe3), -0.32 (d, 4 H, 2JYH ) 2.5 Hz).13C NMR (75.4 MHz, C6D6): δ 180.9 (s, NN′CPh), 139.5 (s, Ph Cipso), 129.5 (d, J ) 153.7 Hz), 128.5 (d, J ) 153.7 Hz), 127.8 (d, J ) 158.6 Hz), 127.7 (d, J ) 161.1 Hz), 125.3 (d, J ) 158.7 Hz, all Ph CH), 60.9 (t, J ) 133.0 Hz, NCH2CH2NMe2), 46.3 (t, J ) 134.2 Hz, NCH2CH2NMe2), 45.9 (q, J ) 133.0 Hz, NMe2), 42.1 (q, J ) 135.4 Hz, NMe2), 31.3 (d, 1JYC ) 36.6 Hz, t, 1JCH ) 95.1 Hz, YCH2), 5.4 (q, J ) 118.3 Hz, CH2SiMe3), 3.4 (q, J ) 118.3 Hz, NSiMe3). Anal. Calcd for C36H70N6Si2YLi (794.18): C, 54.38; H, 8.87; N, 10.57. Found: C, 53.60; H, 9.03; N, 10.27. [PhC(N(CH2)3NMe2)(NSiMe3)]2YCH2Ph (4). To a suspension of YCl3(THF)3.5 (0.45 g, 1.0 mmol) in THF (40 mL) was added solid Li[PhC(N(CH2)3NMe2)(NSiMe3)] Li[C] (0.57 g, 2.0 mmol). The reaction mixture was stirred overnight and then cooled to -40 °C, after which KCH2Ph (0.13 g 1.0 mmol) was added. The mixture was allowed to warm to ambient temperature and stirred for an additional hour. The solvent was removed in vacuo and the residue extracted with pentane (3 × 50 mL). Concentration and cooling to -20 °C yielded 4(pentane)0.5 (0.42 g, 0.57 mmol, 57%) as yellow crystals. The reaction of equimolar amounts of YCl3(THF)3.5 (0.34 g, 0.76 mmol) and Li[C] (0.22 g, 0.76 mmol) with 2 equiv of KCH2Ph (0.2 g, 1.5 mmol) yielded 0.15 g of 4(pentane)0.5 (0.2 mmol, 26%). 1H NMR (300 MHz, C6D6): δ 7.25 (m, 8 H, Ph), 7.17 (m, 4 H, Ph), 7.07 (m, 2 H, Ph), 6.75 (t, 3JHH ) 6.6 Hz, 1 H, Bz p-H), 2.99 (t, 4 H, 3JHH ) 6.9 Hz, NCH2(CH2)2NMe2), 2.31 (br, 2 H, CH2Ph), 2.08 (overlap, 16 H CH2NMe2 and NMe2), 1.49 (br m, 4 H, -CH2-), 0.15 (s, 18 H, NSiMe3). 13C NMR (75.4 MHz, C6D6): δ 179.9 (s, NN′CPh), 154.7(s, Ph Cipso), 138.5(s, Ph Cipso), 128.9 (d, J ) 153.7 Hz), 128.4 (d, J ) 153.5 Hz), 128.1 (d, J ) 159.8 Hz), 126.4 (d, J ) 154.3 Hz), 123.4 (d, J ) 151.3 Hz), 116.0 (d, J ) 158.5 Hz, all Ph CH), 60.0 (t, d, J ) 133.0 Hz, NCH2(CH2)2NMe2), 52.5 (d, 1JYC ) 29.3 Hz, t, 1JCH ) 121.9 Hz, YCH2Ph), 47.2 (t, J ) 133.0 Hz, N(CH2)2CH2NMe2), 45.8 (q, J ) 134.2 Hz, NMe2), 29.2 (t, J ) 124.4 Hz, NCH2CH2CH2NMe2), 2.6 (q, J ) 117.0 Hz, NSiMe3). Anal. Calcd for C37H59N6YSi.(C5H12)0.5 (732.99 + 36.07): C, 61.96; H, 8.52; N, 10.93; Y, 11.56. Found: C, 61.66; H, 8.51; N, 10.45; Y, 10.72. K[Me2N(CH2)2NSiMe3]. A solution of Me2N(CH2)2NHSiMe3 (7.0 g, 43.2 mmol) and styrene (2.3 g, 21.9 mmol) in ether (60 mL) was stirred with potassium (1.7 g, 43.0 mmol) for 24 h, after which almost all the potassium had reacted. The volatiles were removed in vacuo, and the powdery residue was extracted with ether (3 × 100 mL). Concentration and cooling to -20 °C yielded K[Me2N(CH2)2NSiMe3] (1.67 g, 8.35 mmol, 20%) as an off-white powder. 1H NMR (300 MHz, C6D6): δ 3.40 (br, 2 H, NCH2CH2NMe2), 2.26 (t, 3JHH ) 5.1 Hz, 2 H, NCH2CH2NMe2), 2.00 (s, 6 H NMe2), 0.19 (s, 9 H, NSiMe3).

Organometallics, Vol. 19, No. 16, 2000 3203 Table 5. Crystallographic Data for 1 and 2a formula mol wt cryst syst space group a, Å b, Å c, Å R, deg β, deg γ, deg V, Å3 Z Dcalc, g cm-3 F(000) µ(Mo KR j ), cm-1 cryst size, mm

horz, vert aperture, mm ref reflns rms dev in % drift correction X-ray exposure time, h total data unique data data with criterion: (Fo g 4.0σ(Fo)) number of reflns (Fo2 g 0) no. of refined params wR(F2)a weighting scheme:b a, b R(F)c goodness of fit min, max resid density, e/Å3 (∆/σ)max final cycle wR(F2)

2a

C37H85ClLiN2O3Si4Y 849.74 momoclinic P21/n (No. 14) 13.422(1) 17.781(1) 21.269(1)

5074.0(5) 4 1.112 1840 13.3 0.10 × 0.25 × 0.50

C28H62N3Si5Y 670.15 triclinic P1 h (No. 2) 9.350(5) 10.724(1) 20.363(5) 88.71(4) 81.68(3) 75.09(2) 1952.0(12) 2 1.140 720 16.67 0.25 × 0.30 × 0.33

Data Collection Mo KR h 0.71073 130 1.15, 25.5 ω/2θ 0.90 + 0.34 tan θ -16:16, 0:21, 0:25 3.2 + tan θ; 4.0

Mo KR h 0.71073 130 1.01, 27.0 ω/2θ 1.15 + 0.34 tan θ -11:11, -13:13, -25:0 3.2 + tan θ; 4.0

024, 2.1 1-33, 0.23 3-12, 0.61 1.000-1.037 132.0

-114, 2.2 0-2-4, 0.8 -2-10, 3.1 0.984-1.000 181.0

10 010 9392 4912

8709 8465 6480

Refinement 9386

8465

461 0.2060 0.1077, 0.0

582 0.1441 0.0782, 2.57

0.0793 0.975 -0.55, 0.99(10)

0.0488 1.058 -1.76, 1.08(12)

4.0σ(Fo).

) )

K[PhC(N(CH2)2NMe2)(NSiMe3)] (K[B]). A procedure was followed similar to that for Li[B] starting from K[Me2N(CH2)2NSiMe3] (1.5 g, 5.5 mmol) and benzonitrile (0.5 mL, 5.5 mmol), yielding 1.9 g of K[B] (6.2 mmol, 83%). 1H NMR (300 MHz, C6D6): δ 7.23 (m, 5 H, Ar), 3.10 (t, 2 H, 3JHH ) 5.4 Hz, NCH2CH2NMe2), 2.22 (br, 2 H, NCH2CH2NMe2), 1.86 (s, 6 H NMe2), 0.09 (s, 9 H, NSiMe3). 13C{1H} NMR (75.4 MHz, C6D6): δ 173.5 (NN′CPh), 145.1 (Ph Cipso), 128.7 (o-Ph), 126.8 (m-Ph), 125.8 (p-Ph), 63.4 (NCH2CH2NMe2) 48.5 (NCH2CH2NMe2), 45.19 (NMe2), 4.0 (NSiMe3). [PhC(N(CH2)2NMe2)(NSiMe3)]2YCH2Ph(THF) (5). To a slurry of 0.23 g of YCl3(THF)3.5 (0.50 mmol) in 30 mL of THF was added 0.30 g of K[B] (1.0 mmol). The mixture was stirred overnight, then cooled to - 40 °C, and 0.07 g (0.50 mmol) of KCH2Ph was added. The mixture was allowed to warm to ambient temperature and was stirred for an additional 2 h. The solvent was removed in vacuo, and the residue was stripped of remaining THF by stirring with pentane, which was subsequently pumped off. Extraction with pentane (2 × 40 mL), concentrating, and cooling the extract to -20 °C

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Organometallics, Vol. 19, No. 16, 2000

Bambirra et al.

Table 6. Crystallographic Data for 3a and 4 3a formula mol wt cryst syst space group a, Å b, Å c, Å R, deg β, deg γ, deg V, Å3 Z Dcalc, g cm-3 F(000) µ(Mo KR j ), cm-1 cryst size, mm radiation λ(Mo KR), Å T, K θ range, deg scan type ∆ω data set horz, vert aperture, mm ref reflns rms dev in %

C42H62LiN6Si2Y 803.01 momoclinic P21/n (No. 14) 19.695(3) 19.968(3) 23.502(3)

C37H56N6Si2Y.(C5H12)0.5 769.07 triclinic P1 h (No. 2) 8.762(3) 11.350(2) 22.234(4) 80.56(1) 101.37(1) 89.39(2) 79.39(2) 9061(2) 2145.3(9) 8 2 1.177 1.196 3408 822 13.71 14.5 0.15 × 0.19 × 0.28 0.20 × 0.25 × 0.50 Data Collection Mo KR h 0.71073 130 1.02, 25.0 ω/2θ 1.15 + 0.34 tan θ 0:23, 0:23, -27:27 3.2 + tan θ; 4.0

Mo KR h 0.71073 130 1.85, 25.0 ω/2θ 0.80 + 0.34 tan θ 0:10, -13:13, -26:26 3.2 + tan θ; 4.0

3-33, 1.3 33-3, 0.8 -333, 1.1 0.992-1.007 202.9

11-5, 1.7 222, 7.8 201, 7.5 1.000-1.058 107.6

drift correction X-ray exposure time, h total data 17 183 unique data 15 918 data with criterion: 7483 (Fo g 4.0 σ(Fo)) number of reflns (Fo2 g 0) no. of refined params wR(F2)a weighting scheme:b a, b R(F)c goodness of fit min, max resid density, e/Å3 (∆/σ)max final cycle a

wR(F2)

4

8100 7554 5784

Refinement 15 914

7554

957

449

0.1998 0.0907, 0.0

0.1761 0.1105, 0.1840

0.0840 0.949 -1.34, 0.82(11)

0.0586 1.115 -1.18, 1.25(11)

4.0σ(Fo).

(75.4 MHz, C6D6): δ 178.9 (s, NN′CPh), 155.2 (s, Ph Cipso), 138.9 (s, Ph Cipso), 129.4 (d, J ) 153.8 Hz, o-Ph), 128.3 (d, J ) 161 Hz, 2 × Ph CH), 126.9 (d, J ) 152.5 Hz, m-Ph), 122.9 (d, J ) 152.5 Hz, Ph CH), 115.9 (d, J ) 158.6 Hz, p-Ph), 68.8 (t, J ) 145.2 Hz, THF), 62.1 (t, J ) 133.0 Hz, NCH2CH2NMe2), 52.4 (d, 1JYH ) 28.0 Hz, t, 1JCH ) 123.7 Hz, YCH2Ph), 45.9 (t, J ) 134.0 Hz, NCH2CH2NMe2), 45.5 (q, J ) 133.0 Hz, NMe2), 25.6 (t, J ) 131.8 Hz, THF), 3.0 (q, J ) 118.4 Hz, NSiMe3). Crystal Structure Determinations. Suitable crystals of 1, 2a, 3a, and 4‚(pentane)0.5 were mounted on a glass needle in a drybox and transferred under inert atmosphere into the cold nitrogen stream of an Enraf-Nonius CAD4-F diffractometer (monochromated Mo KR). Accurate cell parameters and an orientation matrix were determined from the setting of 22 reflections in the ranges 15.00° < θ < 20.33° (1), 16.79° < θ < 21.62° (2a), 14.85° < θ < 18.96° (3b), and 16.52° < θ < 20.42° (4). Reduced cell calculations did not indicate any higher lattice symmetry.27 Crystal data and details on data collection and refinement are presented in Tables 5 and 6. Intensity data were corrected for Lorentz and polarization effects, but not for absorption. The structures were solved using Patterson methods, and the models were extended by direct methods applied to difference structure factors (DIRDIF28). All calculations were performed on a HP9000/735 computer with the program packages SHELXL29 (least-squares refinement) and PLATON30 (calculation of geometric data and the ORTEP illustrations). For 1, 3a, and 4 the hydrogen atoms were refined riding on their carrier atoms, and the methyl groups were refined as rigid groups that were allowed to rotate freely. For 2a all hydrogen atom positional and isotropic thermal parameters were refined. In 1 the THF molecules bound to Li show significant disorder, which was difficult to treat with disorder models. Ultimately, restraints were used in the final refinement (in which the disorder is compensated by the large thermal displacement parameters). In 4 the n-pentane solvent molecule is disordered, with the central carbon atom located at the inversion center. A 50:50 disorder model for C(38) was used in the refinement.

Acknowledgment. This investigation was generously supported by Exxon Chemical Company. Supporting Information Available: Full crystallographic details, positional and thermal parameters, and distances and angles for 1, 2a, 3a, and 4. This material is available free of charge via the Internet at http://pubs.acs.org. OM0001063 0. w ) R(F) ) ∑ b

yielded 5 (0.23 g, 0.31 mmol, 60%) as a yellow microcrystalline solid. 1 H NMR (300 MHz, C6D6): δ 7.25-7.05 (m, 14 H, Ph), 6.66 (br t, 1 H, Bz p-H), 3.77 (m, 4 H, THF), 3.04 (t, 4H, 3JHH ) 6.6 Hz, NCH2CH2NMe2), 2.26 (d, 2JYH ) 2.7 Hz, 2 H YCH2Ph), 2.20 (t, 3JHH ) 6.6 Hz, 4 H, NCH2CH2NMe2), 2.10 (s, 12 H NMe2), 1.47 (m, 4 H, THF), 0.13 (s, 18 H, NSiMe3). 13C NMR

(27) Spek, A. L. J. Appl. Crystallogr. 1988, 21, 578. (28) Beurskens, P. T.; Beurskens, G.; Bosman, W. P.; De Gelder, R.; Garcı´a-Granda, S.; Gould, R. O.; Israe¨l, R.; Smits, J. M. M. The DIRDIF-97 program system; Crystallography Laboratory; University of Nijmegen: Nijmegen, The Netherlands, 1997. (29) Sheldrick, G. M. SHELX-97. Program for the Solution and Refinement of Crystal Structures; University of Go¨ttingen: Go¨ttingen, Germany, 1997. (30) Spek, A. L. PLATON. Program for the Automated Analysis of Molecular Geometry, Version March 1998; University of Utrecht: Utrecht, The Netherlands.